U.S. patent application number 15/509558 was filed with the patent office on 2017-10-26 for method for producing 3-chloro-2-hydroxypropyl (meth)acrylate and method for producing glycidyl (meth)acrylate.
This patent application is currently assigned to Mitsubishi Rayon Co., Ltd.. The applicant listed for this patent is Mitsubishi Rayon Co., Ltd.. Invention is credited to Hiroyuki MORI, Naoshi MURATA.
Application Number | 20170305870 15/509558 |
Document ID | / |
Family ID | 55580810 |
Filed Date | 2017-10-26 |
United States Patent
Application |
20170305870 |
Kind Code |
A1 |
MURATA; Naoshi ; et
al. |
October 26, 2017 |
METHOD FOR PRODUCING 3-CHLORO-2-HYDROXYPROPYL (METH)ACRYLATE AND
METHOD FOR PRODUCING GLYCIDYL (METH)ACRYLATE
Abstract
To reduce formation of side products and to enhance a
selectivity rate in a method for producing 3-chloro-2-hydroxypropyl
(meth)acrylate and in a method for producing glycidyl
(meth)acrylate. The present invention is characterized by a method
for producing 3-chloro-2-hydroxypropyl (meth)acrylate through a
reaction of (meth)acrylic acid and epichlorohydrin; more
specifically, the reaction is carried out by using 0.5 to 2 mol of
epichlorohydrin relative to 1 mol of (meth)acrylic acid, and by
adding epichlorohydrin to (meth)acrylic acid in the presence of a
catalyst. Also, the present invention is characterized by a method
for producing glycidyl (meth)acrylate through a reaction of
3-chloro-2-hydroxypropyl (meth)acrylate and a basic carbonate
compound in a polar solvent.
Inventors: |
MURATA; Naoshi; (Hiroshima,
JP) ; MORI; Hiroyuki; (Hiroshima, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsubishi Rayon Co., Ltd. |
Tokyo |
|
JP |
|
|
Assignee: |
Mitsubishi Rayon Co., Ltd.
Tokyo
JP
|
Family ID: |
55580810 |
Appl. No.: |
15/509558 |
Filed: |
August 4, 2015 |
PCT Filed: |
August 4, 2015 |
PCT NO: |
PCT/JP2015/072067 |
371 Date: |
March 8, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 67/08 20130101;
C07C 67/26 20130101; C07D 303/16 20130101; C07D 301/16 20130101;
C07C 69/54 20130101; C07D 301/30 20130101; C07B 61/00 20130101 |
International
Class: |
C07D 301/16 20060101
C07D301/16; C07C 67/26 20060101 C07C067/26 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 22, 2014 |
JP |
2014-192145 |
Claims
1. A method for producing 3-chloro-2-hydroxypropyl (meth)acrylate,
comprising: reacting (meth)acrylic acid and epichlorohydrin,
wherein 0.5 to 2 mol of epichlorohydrin per 1 mol of (meth)acrylic
acid is set for reaction, and epichlorohydrin is added to
(meth)acrylic acid in the presence of a catalyst.
2. A method for producing glycidyl (meth)acrylate, comprising:
reacting 3-chloro-2-hydroxypropyl (meth)acrylate and a basic
carbonate compound in a polar solvent.
3. The method for producing glycidyl (meth)acrylate according to
claim 2, wherein the polar solvent is an alcohol.
4. The method for producing glycidyl (meth)acrylate according to
claim 3, wherein the alcohol is a C1-C10 aliphatic hydrocarbon
alcohol.
5. The method for producing glycidyl (meth)acrylate according to
claim 4, wherein the alcohol is at least one kind selected from the
group consisting of 1-propanol, 2-propanol, 1-butanol, 2-butanol
and t-butanol.
6. The method for producing glycidyl (meth)acrylate according to
claim 2, wherein the basic carbonate compound comprises a Group 1
or Group 2 metal.
7. The method for producing glycidyl (meth)acrylate according to
claim 2, wherein the basic carbonate compound is at least one kind
selected from the group consisting of potassium carbonate, rubidium
carbonate and cesium carbonate.
8. The method for producing glycidyl (meth)acrylate according to
claim 6, wherein the basic carbonate compound is at least one kind
selected from among the group consisting of potassium carbonate,
rubidium carbonate and cesium carbonate.
9. A method for producing glycidyl (meth)acrylate, comprising: (1)
a step for producing 3-chloro-2-hydroxypropyl (meth)acrylate
through a reaction of 0.5 to 2 mol of epichlorohydrin per 1 mol of
(meth)acrylic acid, by adding epichlorohydrin to (meth)acrylic acid
in the presence of a catalyst; and (2) a step for producing
glycidyl (meth)acrylate by reacting the 3-chloro-2-hydroxypropyl
(meth)acrylate and a basic carbonate compound in a polar
solvent.
10. The method for producing glycidyl (meth)acrylate according to
claim 3, wherein the basic carbonate compound comprises a Group 1
or Group 2 metal.
11. The method for producing glycidyl (meth)acrylate according
claim 4, wherein the basic carbonate compound comprises a Group 1
or Group 2 metal.
12. The method for producing glycidyl (meth)acrylate according to
claim 5, wherein the basic carbonate compound comprises a Group 1
or Group 2 metal.
13. The method for producing glycidyl (meth)acrylate according to
claim 3, wherein the basic carbonate compound is at least one kind
selected from the group consisting of potassium carbonate, rubidium
carbonate and cesium carbonate.
14. The method for producing glycidyl (meth)acrylate according to
claim 4, wherein the basic carbonate compound is at least one kind
selected from the group consisting of potassium carbonate, rubidium
carbonate and cesium carbonate.
15. The method for producing glycidyl (meth)acrylate according to
claim 5, wherein the basic carbonate compound is at least one kind
selected from the group consisting of potassium carbonate, rubidium
carbonate and cesium carbonate.
Description
TECHNICAL FIELD
[0001] The present invention relates to a method for producing
3-chloro-2-hydroxypropyl (meth)acrylate, and to a method for
producing glycidyl (meth)acrylate.
BACKGROUND ART
[0002] In a method typically employed for synthesizing glycidyl
(meth)acrylate, epichlorohydrin is used as raw material. Such
synthesis may be roughly sorted into the two methods described
below.
[0003] A first method is to synthesize glycidyl (meth)acrylate by
reacting epichlorohydrin and an alkali metal salt of (meth)acrylic
acid in the presence of a catalyst (Patent Literature 1); and a
second method is to synthesize glycidyl (meth)acrylate by reacting
epichlorohydrin and (meth)acrylic acid in the presence of a
catalyst so as to generate 3-chloro-2-hydroxypropyl (meth)acrylate
as an intermediate, which is then subjected to a ring-closing
reaction (dehydrochlorination reaction) in an alkaline solution
(Patent Literature 2).
CITATION LIST
Patent Literature
[0004] Patent Literature 1: JP H07-2818A
[0005] Patent Literature 2: JP H07-118251A
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006] However, the method described in Patent Literature 1
requires a process and a facility for producing alkali metal salts
of (meth)acrylic acid, thus increasing the production cost of
glycidyl (meth)acrylate.
[0007] The method described in Patent Literature 2 is known to
result in a lower yield than the method in Patent Literature 1 when
producing glycidyl (meth)acrylate, because of the lower selectivity
rates in a first phase conducted by reacting epichlorohydrin and
(meth)acrylic acid as well as in a second phase conducted through a
ring-closing reaction in an alkaline solution.
[0008] In addition, since epichlorohydrin as raw material contains
highly reactive epoxy groups, various side reactions may progress.
Thus, suppressing side reactions and reducing formation of
resultant side reaction products are the issues to be solved. It
has been desired to reduce formation of side-reaction products
throughout the entire process.
[0009] Considering the above, the main objective of the present
invention is to provide a method capable of reducing formation of
side-reaction products, while enhancing selectivity during
reactions, for producing 3-chloro-2-hydroxypropyl (meth)acrylate
and glycidyl (meth)acrylate.
Solutions to the Problems
[0010] The inventors of the present invention have carried out
intensive studies on problems associated with conventional
technology and found that the above objective is achieved by
reacting epichlorohydrin and (meth)acrylic acid under specific
conditions. Accordingly, the present invention has been
completed.
[0011] Namely, an aspect of the present invention is a method for
producing 3-chloro-2-hydroxypropyl (meth)acrylate by reacting
(meth)acrylic acid and epichlorohydrin. In such a method, 0.5 to 2
mol of epichlorohydrin per 1 mol of (meth)acrylic acid is set for a
reaction, where epichlorohydrin is added to (meth)acrylic acid in
the presence of a catalyst.
[0012] Also, another aspect of the present invention is a method
for producing glycidyl (meth)acrylate by reacting
3-chloro-2-hydroxypropyl (meth)acrylate and a basic carbonate
compound in a polar solvent.
[0013] Furthermore, yet another aspect of the present invention is
a method for producing glycidyl (meth)acrylate including the
following steps (1) and (2):
[0014] (1) a step for producing 3-chloro-2-hydroxypropyl
(meth)acrylate through a reaction of 0.5 to 2 mol of
epichlorohydrin per 1 mol of (meth)acrylic acid, by adding
epichlorohydrin to (meth)acrylic acid in the presence of a
catalyst; and
[0015] (2) a step for producing glycidyl (meth)acrylate by reacting
3-chloro-2-hydroxypropyl (meth)acrylate and a basic carbonate
compound in a polar solvent.
Effects of the Invention
[0016] According to the present invention, 3-chloro-2-hydroxypropyl
(meth)acrylate and glycidyl (meth)acrylate are produced while
formation of side products is low. Moreover, present invention
provides a method that exhibits high selectivity during the
reactions for producing 3-chloro-2-hydroxypropyl (meth)acrylate and
glycidyl (meth)acrylate.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0017] In the present application, (meth)acrylic acid indicates
methacrylic acid or acrylic acid.
[0018] According to the present invention, glycidyl (meth)acrylate
is obtained through a pathway for producing
3-chloro-2-hydroxypropyl (meth)acrylate. Hereinafter, a step for
producing 3-chloro-2-hydroxypropyl (meth)acrylate is referred to as
"step 1" and a step for producing glycidyl (meth)acrylate is
referred to as "step 2."
[Step 1]: Producing 3-chloro-2-hydroxypropyl (meth)acrylate
[0019] In step 1, 3-chloro-2-hydroxypropyl (meth)acrylate is
produced by reacting epichlorohydrin and (meth)acrylic acid.
[0020] Reaction conditions specified as conditions (A) and (B)
below are employed for the above reaction.
[0021] Condition (A): the reaction is carried out by setting the
amount of epichlorohydrin at 0.5 to 2 mol per 1 mol of
(meth)acrylic acid.
[0022] Condition (B): epichlorohydrin is added to (meth)acrylic
acid in the presence of a catalyst.
[Condition (A)]
[0023] When (meth)acrylic acid and epichlorohydrin are reacted, the
molar ratio is set at 0.5 to 2 mol of epichlorohydrin per 1 mol of
(meth)acrylic acid. The ratio of epichlorohydrin relative to 1 mol
of (meth)acrylic acid is preferred to be 0.6 to 1.5 mol, more
preferably 0.8 to 1.2 mol. Relative to 1 mol of (meth)acrylic acid,
a molar ratio of epichlorohydrin set at 0.5 mol or higher
suppresses side reactions, while a molar ratio of epichlorohydrin
set at 2 mol or lower also suppresses side reactions.
[Condition (B)]
[0024] In the present invention, epichlorohydrin is added to
(meth)acrylic acid in the presence of a catalyst. More
specifically, it is preferred to drop epichlorohydrin into a
reaction vessel where (meth)acrylic acid and a catalyst have been
charged and heated. According to such a method, the reaction is
progressed safely at a high selectivity rate, while formation of
side products is suppressed. By contrast, if epichlorohydrin and a
catalyst are charged in a reaction vessel and heated, and then
(meth)acrylic acid is dropped into the reaction vessel, formation
of diesters increases, resulting in a lower selectivity rate.
[Other Conditions]
[0025] In step 1, the reaction temperature is preferred to be set
at 50 to 150.degree. C., more preferably 60 to 130.degree. C. A
reaction temperature of 50.degree. C. or higher contributes to an
efficient production of 3-chloro-2-hydroxypropyl (meth)acrylate. A
reaction temperature of 150.degree. C. or lower suppresses side
reactions such as polymerization of 3-chloro-2-hydroxypropyl
(meth)acrylate.
[0026] In step 1, the reaction time is not limited to any specific
duration, and is selected appropriately according to the amount of
raw material, reaction temperature and so on. For example, the
reaction time is set for 0.1 to 20 hours, preferably 0.2 to 10
hours, more preferably 0.5 to 5 hours. By setting the reaction time
to be 0.1 hour or longer, the reaction product is obtained at a
higher conversion rate. By setting the reaction time to be 20 hours
or shorter, formation of side products is suppressed.
[Catalyst]
[0027] Any known catalyst may be used as the catalyst in the
reaction of step 1, for example, quaternary ammonium salts or
ion-exchange resins having such salts. Examples of quaternary
ammonium salts are tetraalkylammonium salts such as
tetramethylammonium chloride, tetramethylammonium bromide,
tetraethylammonium chloride, tetraethylammonium bromide, tetrabutyl
ammonium chloride and tetrabutylammonium bromide. A commercially
available strong basic anion exchange resin may be used as the
ion-exchange resin. These catalysts may be used alone, or in
combination thereof.
[0028] The amount of catalyst is not limited specifically. For
example, relative to 1 mol of (meth)acrylic acid, the amount may be
set at 0.0001 to 0.1 mol, preferably 0.0005 to 0.05 mol, more
preferably 0.001 to 0.03 mol. Relative to 1 mol of (meth)acrylic
acid, an amount of catalyst at 0.0001 mol or greater enhances the
reaction rate, while an amount of catalyst at 0.1 mol or less
suppresses formation of side products.
[Step 2]: Producing Glycidyl (meth)acrylate
[0029] In step 2, a reaction of 3-chloro-2-hydroxypropyl
(meth)acrylate and a basic carbonate compound is carried out in a
polar solvent to produce glycidyl (meth)acrylate. By using a
specific kind of basic carbonate compound and a polar solvent as
the solvent, side reactions are suppressed, thus reducing formation
of side products.
[0030] The 3-chloro-2-hydroxypropyl (meth)acrylate produced in step
1 may be used as is, or it may be refined by a known method.
Alternatively, 3-chloro-2-hydroxypropyl (meth)acrylate obtained by
another method or a commercially available kind may be refined and
used if applicable.
[Polar Solvent]
[0031] Examples of a polar solvent are alcohols, ketones, esters,
amides, ethers, halogenated hydrocarbons, dialkyl sulfoxides and
the like. Among them, alcohols are especially preferable.
[Alcohol]
[0032] An alcohol as the solvent is not limited to any specific
kind. Considering availability and solubility, it is preferred to
use a C1.about.C10 aliphatic hydrocarbon alcohol, more preferably a
C1.about.C8 aliphatic hydrocarbon alcohol. Examples of such
alcohols are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
2-butanol, t-butanol, 1-heptanol, 1-hexanol, cyclohexanol,
1-pentanol, 1-octanol, and the like. Considering the boiling point
and availability, 1-propanol, 2-propanol, 1-butanol, 2-butanol,
t-butanol and the like are more preferable. Alcohols may be used
alone or in combination thereof.
[0033] It is sufficient if there is enough alcohol to fluidize a
salt side product into slurry. An alcohol is preferred to be used
0.1 to 100 times, more preferably 0.5 to 50 times, even more
preferably 1 to 20 times, the mass of 3-chloro-2-hydroxypropyl
(meth)acrylate. By setting the amount of alcohol to be at least 0.1
times the mass of 3-chloro-2-hydroxypropyl (meth)acrylate, the salt
side product is efficiently fluidized. By setting the amount of
alcohol to be no greater than 100 times the mass of
3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate is
efficiently refined or the like.
[Basic Carbonate Compound]
[0034] A basic carbonate compound is not limited to any specific
kind as long as it is capable of promoting dehydrochlorination
reactions of 3-chloro-2-hydroxypropyl (meth)acrylate. As for a
basic carbonate compound, those containing Group 1 or Group 2
metals are preferred because they are capable of efficiently
progressing reactions, suppressing side reactions and reducing
formation of side products.
[0035] Examples of such a basic carbonate compound are lithium
carbonate, sodium carbonate, potassium carbonate, rubidium
carbonate, cesium carbonate, magnesium carbonate, calcium
carbonate, and the like. Among them, potassium carbonate, rubidium
carbonate, cesium carbonate and the like are more preferable. Those
basic compounds may be used alone or in combination thereof.
[0036] The amount of basic carbonate compound is not limited
specifically, as long as reactions are progressed efficiently. For
example, relative to 1 mol of 3-chloro-2-hydroxypropyl
(meth)acrylate, the amount is preferred to be 0.1 to 3 mol, more
preferably 0.3 to 2 mol, even more preferably 0.5 to 1.5 mol.
Relative to 1 mol of 3-chloro-2-hydroxypropyl (meth)acrylate, an
amount of basic carbonate compound set at 0.1 mol or greater
enhances the reaction rate, while an amount of basic carbonate
compound set at 3 mol or less suppresses side reactions.
[Reaction Conditions]
[0037] The reaction temperature in step 2 is preferred to be 50 to
150.degree. C., more preferably 60 to 130.degree. C. A reaction
temperature of 50.degree. C. or higher contributes to efficiently
producing glycidyl (meth)acrylate, while a reaction temperature of
150.degree. C. or lower suppresses side reactions such as
polymerization.
[0038] In step 2, the reaction time is not limited to any specific
duration, and is selected appropriately according to the amount of
raw material, reaction temperature and so on. For example, the
reaction time is set to be 0.1 to 20 hours, preferably 0.2 to 10
hours, more preferably 0.5 to 5 hours. By setting a reaction time
to be 0.1 hour or longer, glycidyl (meth)acrylate is obtained at a
higher conversion rate. By setting the reaction time to be 20 hours
or shorter, formation of side products is suppressed.
[Polymerization Inhibitor, Refining or the like]
[0039] A known polymerization inhibitor may be used to suppress
polymerization in steps 1 and 2. Examples of a polymerization
inhibitor are phenol-based inhibitors such as hydroquinone and
p-methoxyphenol; amine-based inhibitors such as phenothiazine; and
N-oxyl-based inhibitors such as
4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (HO-TEMPO). They may
be used alone or in combination thereof.
[0040] The amount of polymerization inhibitor is preferred to be 10
to 10000 mass ppm, more preferably 50 to 5000 mass ppm, relative to
the mass of (meth)acrylic acid in step 1 and relative to the mass
of 3-chloro-2-hydroxypropyl (meth)acrylate in step 2. By setting
the amount of polymerization inhibitor to be at least 10 mass ppm,
polymerization is sufficiently suppressed, while by setting the
amount to be no greater than 10000 mass ppm, a decrease in quality,
for example, coloration of products, is prevented.
[0041] To prevent polymerization, it is preferred to carry out
reactions while introducing bubbles of oxygen or a gas containing
oxygen such as air.
[0042] Also, glycidyl (meth)acrylate related to the present
invention may be extracted or refined if applicable. Extraction and
refining are not limited to any specific methods, and any known
methods may be used. For example, the salt in a reaction mixture
obtained in step 2 may be washed with water to remove unwanted
components. Alternatively, the reaction mixture may be filtered to
remove unwanted components. After washing with water or filtering,
crude glycidyl (meth)acrylate contained in a solution is extracted
through distillation so that highly purified glycidyl
(meth)acrylate is obtained.
EXAMPLES
[0043] In the following, the present invention is described in
detail by referring to the examples. However, the present invention
is not limited to those examples. The compound in each of examples
and comparative examples was analyzed through gas chromatography
(GC). Example 1 relates to the production of
3-chloro-2-hydroxypropyl (meth)acrylate, and Examples 2-4 relate to
the production of glycidyl (meth)acrylate.
Example 1
[0044] A 300-mL four-necked flask equipped with a thermometer, an
air inlet tube, a stirring blade, a dropping funnel and a cooling
tube was prepared and charged with 86.09 grams (1.0 mol) of
methacrylic acid, 0.01 grams of an HO-TEMPO benzoate as the
polymerization inhibitor, and 0.548 grams (0.005 mol) of
tetramethylammonium chloride as the catalyst. In the dropping
funnel, 101.78 grams (1.1 mol) of epichlorohydrin was filled.
[0045] Air was introduced into the flask at a rate of 10 mL/min.,
and the mixture in the flask was heated to 90.degree. C. using an
oil bath while being stirred. The epichlorohydrin started dropping
when the temperature of the mixture reached 90.degree. C., and
dropped out into the flask in an hour. After the completion of
dropping, the reaction mixture was stirred for 4 hours while its
temperature was kept at 90.degree. C.
[0046] When the reaction mixture was analyzed by GC, peak area
percentages (%) of the composition were 84.612% of
3-chloro-2-hydroxypropyl methacrylate, 0.975% of glycidyl
methacrylate, 1.106% of methacrylic acid, 4.450% of
epichlorohydrin, 5.115% of diester, 0.364% of triester, 3.377% of
1,3-dichloro-2-propanol, 0.001% of glycidol, and 0.000% of
dichloropropyl methacrylate. The results are shown in Table 1.
Comparative Examples 1 and 2
[0047] In Comparative Examples 1 and 2, the amounts of
epichlorohydrin were changed to 208.19 grams (2.25 mol) and 416.37
grams (4.5 mol) respectively, and the epichlorohydrin amounts were
each added to the four-neck flask all at once. The rest of the
reactions were carried out the same as in Example 1. The results
are shown in Table 1.
Comparative Example 3
[0048] The methacrylic acid in the four-neck flask was replaced
with epichlorohydrin, and the epichlorohydrin in the dropping
funnel was replaced with methacrylic acid. Then, methacrylic acid
was dropped into epichlorohydrin through the dropping funnel. The
rest of the reaction was carried out the same as in Example 1. The
results are shown in Table 1.
Comparative Example 4
[0049] The reaction was carried out the same as in Example 1 except
that the amount of epichlorohydrin charged in the dropping funnel
was changed to 277.590 grams (3.0 mol). The results are shown in
Table 1.
Comparative Example 5
[0050] When the reaction was initiated the same as in Example 1
except that epichlorohydrin was added to the four-neck flask all at
once, the temperature of the reaction mixture rose to 186.degree.
C. in an early stage of the reaction, causing a reflux of the
mixture. Accordingly, the reaction was observed to be out of
control. Since the ratio of "methacrylic acid to epichlorohydrin"
was "1:1.1", which means the amount of epichlorohydrin was less
than those in Comparative Examples 1 and 2, there was no dilution
effect derived from epichlorohydrin. Therefore, it is assumed that
the reactions progressed fast, leaving no time to reduce the heat.
Side products were 12.548% of 1,3-dichloropropanol and 23.586% of
diester. The results are shown in Table 1.
TABLE-US-00001 TABLE 1 Reaction conditions Composition of reaction
mixture (GC: area percentage) (%) methacrylic glycidyl meth- 1,3-
dichloro- 3-chloro-2- acid:epichlorohydrin dropping epichloro-
glyci- meth- acrylic dichloro- propyl hydroxypropyl tri- di- (molar
ratio) funnel hydrin dol acrylate acid 2-propanol methacrylate
methacrylate ester ester Example 1 1:1.1 epichloro- 4.450 0.001
0.975 1.106 3.377 0.000 84.612 0.364 5.115 hydrin Comp. 1:2.25 --
23.520 0.409 25.444 0.000 13.287 1.380 35.534 0.019 0.407 Example 1
Comp. 1:4.5 -- 52.692 0.375 23.298 0.000 11.135 1.086 11.238 0.007
0.169 Example 2 Comp. 1:1.1 methacrylic 1.609 0.000 3.745 0.280
10.294 0.273 57.873 0.473 25.453 Example 3 acid Comp. 1:3.sup.
epichloro- 38.239 0.521 27.472 0.000 13.103 1.404 18.740 0.167
0.354 Example 4 hydrin Comp. 1:1.1 -- 0.373 0.001 1.792 0.018
12.548 0.000 61.051 0.632 23.586 Example 5
Example 2
[0051] A 100-mL four-necked flask equipped with a thermometer, an
air inlet tube, a stirring blade, and a cooling tube was prepared
and charged with 5 grams of the reaction mixture containing
3-chloro-2-hydroxypropyl methacrylate (0.0264 mol of
3-chloro-2-hydroxypropyl methacrylate) obtained in Example 1, 20
grams of isopropyl alcohol (IPA) as the solvent, 2.737 grams
(0.0198 mol) of potassium carbonate as the basic carbonate
compound, and 0.001 grams of an HO-TEMPO benzoate as the
polymerization inhibitor.
[0052] The mixture was heated to a temperature of 80.degree. C.
while being stirred, and the reaction was carried out for 2 hours.
The obtained reaction mixture was analyzed by GC. The area
percentages (%) of the composition were 2.375% of
3-chloro-2-hydroxypropyl methacrylate, 89.149% of glycidyl
methacrylate, 0.000% of methacrylic acid, 6.087% of diester, 1.341%
of triester, 0.011% of 1,3-dichloro-2-propanol, 1.055% of glycidol,
and 0.000% of dichloropropyl methacrylate. The results are shown in
Table 2.
Examples 3 and 4
[0053] Reactions were carried out the same as in Example 2 except
that rubidium carbonate and cesium carbonate were respectively used
as the basic carbonate compound. The results are shown in Table
2.
Comparative Examples 6 and 7
[0054] Reactions were carried out the same as in Example 2 except
that dimethylformamide (DMF) and epichlorohydrin (EPC) were used
respectively as the solvent. The results are shown in Table 2.
Comparative Examples 8-12
[0055] Reactions were carried out the same as in Example 2 except
that basic compounds specified in Table 2 were respectively used.
The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Reaction conditions Composition of reaction
mixture (GC: area percentage) (%) basic 3-chloro-2- compound
glycidyl methacrylic 1,3-dichloro- dichloropropyl hydroxypropyl
solvent carbonate glycidol methacrylate acid 2-propanol
methacrylate methacrylate triester diester Example 2 IPA
K.sub.2CO.sub.3 1.055 89.149 0.000 0.011 0.000 2.357 1.341 6.087
Example 3 IPA Rb.sub.2CO.sub.3 2.550 86.715 0.000 0.021 0.021 0.986
2.950 6.757 Example 4 IPA Cs.sub.2CO.sub.3 2.910 88.950 0.000 0.064
0.000 1.456 0.318 6.302 Comp. DMF K.sub.2CO.sub.3 1.155 56.493
0.000 0.080 0.343 10.599 0.611 30.719 Example 6 Comp. EPC
K.sub.2CO.sub.3 1.614 64.469 0.000 11.734 1.145 16.973 0.351 3.714
Example 7 Comp. IPA LiOH.cndot.H.sub.2O 15.640 30.363 0.000 3.553
0.000 20.457 19.469 10.518 Example 8 Comp. IPA NaOH 3.707 54.471
0.000 0.648 0.011 27.676 3.632 9.855 Example 9 Comp. IPA KOH 4.557
73.489 0.000 0.211 0.000 3.028 4.389 14.326 Example 10 Comp. IPA
DMAP 0.007 3.951 1.855 3.971 0.000 83.633 0.868 5.715 Example11
Comp. IPA Et.sub.3N 0.503 11.704 4.788 1.425 0.000 73.388 0.784
7.408 Example 12
INDUSTRIAL APPLICABILITY
[0056] Glycidyl (meth)acrylate produced by the method related to
the present invention is suitable as raw material for various
coatings, adhesives and binders as well as for a monomer to be used
in various reactions.
* * * * *